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Sulphide Globules in a Porcellanite-Buchite Composite Xenolith from Stromboli

Volcano (Aeolian Islands, Southern Italy): Products of Open-System Igneous
Pyrometamorphism

Article in Minerals · June 2021

DOI: 10.3390/min11060639

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Article

Sulphide Globules in a Porcellanite–Buchite Composite

Xenolith from Stromboli Volcano (Aeolian Islands, Southern
Italy): Products of Open‐System Igneous Pyrometamorphism
Alberto Renzulli 1, Marco Taussi 1,*, Frank J. Brink 2, Stefano Del Moro 3 and Richard W. Henley 4

1 Dipartimento di Scienze Pure e Applicate, Università degli Studi di Urbino Carlo Bo, 61029 Urbino, Italy;
[email protected]
2 Centre for Advanced Microscopy, The Australian National University, Acton, ACT 0200, Australia;

[email protected]
3 Geo.In.Tech. srl, Spin Off—Università degli Studi di Urbino Carlo Bo, 61029 Urbino, Italy;

[email protected]
4 ARC Training Centre for M3D Innovation, Research School of Physics, The Australian National University,

Acton, ACT 0200, Australia; [email protected]

* Correspondence: [email protected]

Abstract: Pyrometamorphism is the highest temperature end‐member of the sanidinite facies (high‐
temperature, low‐pressure contact metamorphism) and comprises both subsolidus and partial
melting reactions which may locally lead to cryptocrystalline‐glassy rocks (i.e., porcellanites and
buchites). A wide range of pyrometamorphic ejecta, with different protoliths from Stromboli
Citation: Renzulli, A.; Taussi, M.; volcano, have been investigated over the last two decades. Among these, a heterogeneous
Brink, F.J.; Del Moro, S.; Henley, (composite) glassy sample (B1) containing intimately mingled porcellanite and buchite lithotypes
R.W. Sulphide Globules in a was selected to be studied through new FESEM–EDX and QEMSCAN™ mineral mapping
Porcellanite–Buchite Composite investigations, coupled with the already available bulk rock composition data. This xenolith was
Xenolith from Stromboli Volcano chosen because of the unique and intriguing presence of abundant Cu–Fe sulphide globules within
(Aeolian Islands, Southern Italy): the buchite glass in contrast with the well‐known general absence of sulphides in Stromboli basalts
Products of Open‐System Igneous or their subvolcanic counterparts (dolerites) due to the oxygen fugacity of NNO + 0.5–NNO + 1 (or
Pyrometamorphism. Minerals 2021,
slightly lower) during magma crystallization. The investigated sample was ejected during the
11, 639. https://doi.org/10.3390/min
Stromboli paroxysm of 5 April 2003 when low porphyritic (LP) and high porphyritic (HP) basalts
11060639
were erupted together. Both types of magmas are present as coatings of the porcellanite–buchite
sample and were responsible for the last syn‐eruptive xenoliths’s rim made of a thin crystalline‐
Academic Editor: Monica Piochi
glassy selvage. The complex petrogenetic history of the B1 pyrometamorphic xenolith is tentatively
Received: 6 May 2021 explained in the framework of the shallow subvolcanic processes and vent system dynamics
Accepted: 15 June 2021 occurred shortly before (January–March 2003) the 5 April 2003 paroxysm. A multistep petrogenesis
Published: 16 June 2021 is proposed to account for the unique occurrence of sulphide globules in this composite
pyrometamorphic xenolith. The initial stage is the pyrometamorphism of an already
Publisher’s Note: MDPI stays neu‐ hydrothermally leached extrusive/subvolcanic vent system wall rock within the shallow volcano
tral with regard to jurisdictional edifice. Successively, fragments of this wall rock were subject to further heating by continuous gas
claims in published maps and institu‐ flux and interaction with Stromboli HP basalt at temperatures above 1000 °C to partially melt the
tional affiliations. xenolith. This is an open system process involving continuous exchange of volatile components
between the gas flux and the evolving silicate melt. It is suggested that the reaction of plagioclase
and ferromagnesian phenocrysts with SO2 and HCl from the volcanic gas during diffusion into the
melt led to the formation of molecular CaCl in the melt, which then was released to the general gas
Copyright: © 2021 by the authors.
Licensee MDPI, Basel, Switzerland.
flux. Sulphide formation is the consequence of the reaction of HCl dissolved into the melt from the
This article is an open access article
gas phase, resulting in the release of H2 into the melt and lowering of fO2 driving reduction of the
distributed under the terms and dissolved SO2.
conditions of the Creative Commons
Attribution (CC BY) license
(https://creativecommons.org/license
s/by/4.0/).

Minerals 2021, 11, 639. https://doi.org/10.3390/min11060639 www.mdpi.com/journal/minerals

Minerals 2021, 11, 639 2 of 21

Keywords: igneous pyrometamorphism; gas–solid reactions; buchite; porcellanite; hydrothermally‐

altered volcanics; sulphide; pyrrhotite; Stromboli; Aeolian Islands

1. Introduction
Pyrometamorphism is a type of thermal metamorphism involving very high
temperatures—often to the point of melting in suitable lithologies at low pressures—that
has been extensively reviewed by Grapes [1]. Pyrometamorphic rocks are micro‐
cryptocrystalline to glassy, as the result of processes of recrystallization and
melting/crystallization under high temperature/low pressure conditions. The term
pyrometamorphism (from the Greek pyr/pyro: fire; meta: change; morph: shape or form) was
first used by Brauns [2] to describe high temperature changes taking place at the
immediate contact of magma and country rocks with or without metasomatic processes.
The high temperatures can be provided by magma (i.e., igneous pyrometamorphism),
spontaneous combustion of coal, carbonaceous sediments, oil and gas (giving rise to the
so called paralavas), or lightning that strikes at the surface. All of these conditions
characterize the sanidinite facies of metamorphism (Figure 1).

Figure 1. The Petrogenetic Grid at low pressure (P < 3 kbar) showing a relationship of igneous pyrometamorphism
(sanidinite facies rocks) with lower temperature contact metamorphism (modified from [1]). P–T estimates of contact
aureole rocks are from Barton et al. [3], wet/dry basalt solidus of various basalt compositions after Yoder and Tilley [4],
wet/dry granite solidus from Tuttle and Bowen [5], andalusite/sillimanite transition (H) from Holdaway [6],
quartz/tridymite/cristobalite inversion curves from Kennedy et al. [7] and Ostrovsky [8].

Following the nomenclature descriptions and definitions given by Grapes [1], the
products of igneous pyrometamorphism principally comprise two rock types:
1. Buchite. A partly to almost completely vitrified rock resulting from intense contact
metamorphism. The term was coined by Mohl [9]—probably after the German
geologist Leopold Von Buch [10]—to describe fused rocks in contact with basalt,
replacing the term basalt jasper. Although then applied to partially melted sandstones
[11], buchite was later used to describe fused pelitic rocks [12].
2. Porcellanite. A light colored, very fine grained, completely recrystallized
pyrometamorphosed clay, marl, or shale—originally named from a naturally baked
clay considered to be a variety of jasper [13] which led to the adoption of the now
obsolete term porcelain–jasper.
Minerals 2021, 11, 639 3 of 21

The additional term “emery” is used by Grapes [1] to describe dark, hard, and dense
granular rock consisting mainly of corundum, spinel, magnetite, and/or ilmenite–
hematite, formed by high (near basaltic magma) temperature metamorphism of laterite or
aluminous (pelitic) sediments.
Non‐modal melting and rapid mineral reaction rates driven by extreme temperature
gradients that vary by several hundred degrees over a few metres or centimetres [1] lead
to the formation of numerous high temperature minerals, many of which are only found
in pyrometamorphic rocks.
Igneous pyrometamorphic rocks are most commonly exposed in contact aureoles of
mafic intrusions where mechanical erosion of wall rocks of suitable composition may lead
to concentrations of xenoliths in sills and dykes, such as observed in thin (up to 6 m wide)
mafic sills and dikes of the Ross of Mull Peninsula, Scotland [14,15], or along the contact
of a steeply dipping pipe‐like body such as Blaue Kuppe, Germany [16]. By contrast, they
rarely can be seen in active volcanoes, mainly because they occur as xenoliths that have
been entrapped by the erupting magma shortly after the occurrence of very high‐T, low‐
P pyrometamorphic reactions.
Among the igneous pyrometamorphic xenoliths that have been found as ejecta from
active volcanoes, Grapes [1] notes the Stromboli samples studied by Salvioli–Mariani et
al. [17] and interpreted as derived from the crustal basement (metapelites) below the
volcano. By contrast, igneous pyrometamorphic xenoliths affected by vapour–phase
crystallization are reported at Vesuvius, Italy (indialite–bearing; [18]) and Mt. Ruapehu
volcano in New Zealand (osumilite– and indialite–bearing; [19]). Grapes [1] also
emphasized that the protoliths of the pyrometamorphic xenoliths found in White Island
volcano, New Zealand [19,20] are acid–sulphate hydrothermally‐altered vent andesitic
breccia and tuff. Indeed, hydrothermally‐altered rocks may strongly resemble pelites in
terms of their bulk rock chemistry and therefore are potential lithologies that might be
transformed into igneous pyrometamorphic rocks. This is the case for most of the
Stromboli buchite ejecta studied by Del Moro et al. [21] that often contain relicts of
porphyritic textures. Del Moro et al. [21] argue that the likely source rock for these buchite
ejecta was a member of the Upper Vancori volcanic sequence underlying the
Neostromboli and Recent Stromboli edifice that had undergone extensive leaching before
being pyrometamorphosed by the present‐day basalt along the magma conduit walls. The
leaching is due to the persistent activity of Stromboli volcano with eruptions of pyroclastic
material (basaltic scoriae, lapilli and ash) that normally accumulate within the crater area
(also called “crater terrace”, where several active vents are always present) and are
continuously subject to burial, reheating and intense chemical alteration due to the
incessant degassing of the underlying magma system. A suite of anhydrite‐bearing lapilli
tuff ejecta from Stromboli studied by Del Moro et al. [22] may be interpreted as related to
heterogenous gas (SO2) reactions with Ca‐bearing minerals in low pressure solfataric
alteration environment deposits (in and below the crater terrace), at temperatures from
600 to above 800 °C, as suggested by Fegley and Prinn [23], Ayris et al. [24], Henley et al.
[25], and Henley and Seward [26]. As recently demonstrated by Henley and Fischer [27],
sub‐surface mineral–gas reactions between common calcic minerals and SO2 to produce
anhydrite and reduced sulphur exert a profound control on the redox state and total
sulphur concentration of high temperature volcanic gases.
Among the igneous pyrometamorphic ejecta of Stromboli already described by Del
Moro et al. [21], this research focuses on the composite xenolith B1 (erupted during the 5
April 2003 paroxysm) which is a mixture of white porcellanite and dark buchite (Figure
2). Both the volatile‐rich, low porphyritic (LP) basaltic magma (generally involved in the
paroxysms of Stromboli) and the high porphyritic (HP) basalt (i.e., the magma
characterizing the persistent activity and commonly stored in the uppermost part of the
subvolcanic system) are found as a mantle of the investigated pyrometamorphic xenolith
B1. We report new micro‐analytical data (FESEM–EDX and QEMSCANTM) in conjunction
with bulk rock analyses of this sample from Del Moro et al. [21]. Glass of the buchite
Minerals 2021, 11, 639 4 of 21

portion of B1 is uniquely crowded with microspheres of Fe–Cu sulphides (hereafter

globules) otherwise not present in modern (and past) Stromboli eruptive products
because of the oxygen fugacity of the present‐day Stromboli magma (at least for the low
porphyritic basalts as described in Section 2) being between NNO + 0.5 and NNO + 1 [28–
31]. Understanding of the formation of these recently discovered immiscible sulphide
globules requires development of a more complex multistage petrogenetic history of the
porcellanite–buchite xenolith, with respect to the simple two‐stage interpretation (i.e.,
closed system igneous pyrometamorphism on hydrothermally altered volcanics of the
edifice cone) previously proposed by Del Moro et al. [21] for the shallow buchite suite
ejecta of Stromboli. To form the multiphase quenched sulphide globules (S−2), a relative
change in the redox state of S is necessary during the evolution of the buchite ejecta and
therefore an open system igneous pyrometamorpysm is needed, emphasizing the role
played, besides magma, by high temperature gas–solid reactions (between SO2–HCl gas
and calcium silicate phase). Sulphide globules were also recognized (but not analysed) by
Salvioli‐Mariani et al. [17] in another vesicle–rich buchite ejecta sample from Stromboli
(sample PST 107), and the presence of sulphides in lithotypes resulting from
pyrometamorphism is common [1].

Figure 2. Two fragments of the composite B1 xenolith consisting of white porcellanite and dark
buchite. Cuspate–convolute contacts between porcellanite and buchite portions are highlighted, as
well as the juvenile basalt coating the sample. Both HP (highly porphyritic, black scoria) and LP
(low porphyritic, highly vesicular “golden” pumice) are emphasized, as distinct magmas or mingled
with each other. It is worth noting that the LP basalt is only involved during the paroxysmal
eruption of Stromboli such as that of the 5 April 2003 when the porcellanite–buchite xenolith
erupted.

2. Geology and Magmatism of Stromboli Volcano

Stromboli is a stratovolcano of the Aeolian Islands (Tyrrhenian Sea, Italy; Figure 3)
that rises 924 m a.s.l. and represents the emergent part of a ca. 3 km high edifice. The
subaerial evolution of Stromboli is the result of constructional effusive and explosive
activity in the last 100 ka (Paleostromboli, Vancori, Scari, Neostromboli, and Recent
Stromboli periods), also coupled with destructive phases of caldera and sector collapses
[32–35], whereas the islet of Strombolicchio (the remnant of a volcanic neck) shows an
older age of ca. 200 ka (Figure 3a). This volcano is the archetype for Strombolian eruptions
and is characterized by persistent activity, mainly consisting of mild intermittent
explosions and relative accumulation of high porphyritic (HP) black scoria (shoshonitic
basalts with plagioclase + olivine + clinopyroxene phenocrysts/microlites ad
Minerals 2021, 11, 639 5 of 21

cryptocrystalline to glassy groundmass), lapilli and ash near the summit craters,
accompanied by constant and abundant degassing [22,36,37]. The HP magma, stored at a
relatively shallow depth, can also periodically outpour as lava flows, whereas gas‐rich,
low porphyritic (LP), and deeper basalt, with whole rock compositions poorly differing
from that of the HP scoria, can occasionally erupt during more violent explosive episodes
(small and large‐scale paroxysms) as highly vesicular “golden pumices” (from their
yellowish‐brownish colour) commonly mingled with HP products [37–41].

Figure 3. (a) Simplified geological map of the Stromboli volcano (modified after [33]). Neostromboli interval of activity is
also in agreement with recent stratigraphic and volcanological reconstruction of Vezzoli et al. [42] and new paleomagnetic
datings of Risica et al. [43]. The yellow star indicates the sampling point of the B1 porcellanite–buchite xenolith that was
erupted during the 5 April 2003 paroxysm of Stromboli; red dashed lines represent the cross–sections X–Y and X–Z
reported in (b); Lat[°] and Lon [°] stand for Latitude and Longitude in decimal degrees, respectively (coordinate system
WGS84); (b) DC resistivity tomograms (in ohm∙m) along two profiles of Stromboli volcano (X–Y and X–Z) emphasize the
extension of the hydrothermal system outlined by low values (15–50 ohm∙m) of electrical resistivity (redrawn from [44]).
The shallow vents/conduit system is emphasized by a dashed rectangle, it being the place where the igneous
pyrometamorphic processes of Stromboli, as those described for the investigated B1 xenolith, may commonly occur.
Minerals 2021, 11, 639 6 of 21

Stromboli mantle‐derived basaltic magmas rise into a thinned continental crust,

which, according to geophysical investigations, is defined by a Moho located at a depth
of 14.8 km, where S‐wave mantle velocities reach 4.0 km/s [45]. Several authors have
suggested the presence of at least two crustal levels of storage and crystallization of
magmas in the present‐day magma plumbing system of Stromboli [29,31,38,39,46,47]: a
deeper reservoir located between 6–7 and 9–11 km, refilled by ascending mantle‐derived
basaltic magmas and then rising as LP basalts, and a shallower zone at depth <3 km (HP
basalts) that feeds the persistent mild explosive activity.
The study of a wide range of undeformed mafic cumulates and mylonitic gabbro
cognates [48–50], monzonites [51,52], dolerites [53], intrusive, contact metamorphic to
pyrometamorphic xenoliths [17,21,54–58] within Stromboli’s subaerial extrusive rocks
strongly enhanced understanding of the volcanic plumbing system from deep to shallow
levels. Investigations of partially melted felsic intrusive xenoliths of Stromboli also
emphasized similarities with the granitoids and metapelite–quartzite sequences of the
Calabria–Peloritani arc [55]. All of the above lithologies represent the magma–wall rocks
of the Stromboli magmatic plumbing system from the deeper to the shallower crustal
levels, including through the volcano cone where the magma conduit wall rocks are
instead represented by subvolcanic lithologies and extrusives of the edifice itself and their
hydrothermally‐altered counterparts.

2.1. Stromboli Degassing and Hydrothermal System

The crater area of Stromboli is affected by continuous gas emission (e.g., [59–61]). The
visible surface expression of passive degassing of the magma, resulting from the open–
vent system, coexists with active degassing [62] associated with either (i) explosions and
(ii) puffing, this latter being the typical degassing mode of the volcano and consisting of
the emission of small over‐pressurized gas jets/pockets [63]. The volcano continuously
degasses SO2 at rates from about 150 to over 600 t∙d−1 [59] and from a few hundred to more
than 10,000 t∙d−1 of CO2 [60] depending upon the periods of activity of the volcano. The
compositional features of Stromboli’s gas emissions result from the mixing of gases
continuously sourced by (i) degassing of dissolved volatiles in the porphyritic magma
filling the uppermost dyke–conduit system and (ii) CO2–rich gas bubbles, originating at
depths >4 km (P > 100 MPa) of the plumbing system. Changes in magma convection rate
or gas content and/or a structural/tectonic control on the rate of gas bubble supply from
depth are considered at the base of the striking variability in Stromboli’s gas emissions
[60]. The overall composition of the gas emitted by Stromboli, ignoring minor
components, is dominated by H2O (48–98 mol%; mean 80%), CO2 (2–50 mol%; mean 17%)
and SO2 (0.2–14 mol%; mean 3%) [64], closely resembling the typical composition of
volcanic gases from arc‐settings, though sharing with nearby Etna volcano a characteristic
of CO2 enrichment [65]. Halogen concentrations (HCl, HF) in volcanic gas appear to vary
with respect to SO2 and CO2 as a function of stages in the eruptive cycle [66].
The shallow active hydrothermal system of Stromboli has been studied by many
authors (e.g., [44,61,67–72]) via temperature, spontaneous potential field anomalies, CO2
emissions’ measurements, and passive seismic studies monitoring. This hydrothermal
system, highlighted by a conductive body with electrical resistivity in the range 15–50
ohm∙m, is located in the central part of the volcanic edifice with an extension in both the
northeast and east directions (Figure 3b) [44].
While many data are available on the volcanic gas composition and emission rates of
volcanic gas and gaseous discharge from the hydrothermal system of Stromboli, the only
published data, to the best of our knowledge, on Stromboli fumarolic encrustations and
sublimates are from Coradossi and Corsini [73]. These authors found: (i) aragonite
deposits in the relatively low‐T fumarolic zone, (ii) gypsum, anhydrite and pickeringite
(magnesium aluminum sulphate) as sublimates from medium‐T steam emissions, and (iii)
salammoniac, halite, sylvite and alunite in the highest‐T fumaroles. Anhydrite
precipitation, both in vesicles and as rims of clinopyroxenes (thicknesses on the order of
Minerals 2021, 11, 639 7 of 21

tens of μm) together with orthopyroxene, magnetite and silica–rich glass, were also found
in lapilli tuff ejecta of Stromboli [22] as the result of SO2 gas reaction with clinopyroxene
phenocrysts. Anhydrite derived by the degassed SO2 reactions with diopside at high
temperatures (>600 °C) was experimentally demonstrated by Li et al. [74].

2.2. Stromboli Hydrothermal‐Rock Ejecta

In the hydrothermally‐altered ejecta of Stromboli that experienced weak to moderate
alteration, the original porphyritic texture of the Stromboli volcanic rocks is still clearly
recognizable [21]: mafic phenocrysts are oxidized and feldspars have not experienced a
high degree of dissolution or alteration. XRD analyses of these ejecta show the presence
of Ca–sulphate or hydrous Ca–sulphate, cristobalite and hematite [21], and mass–balance
calculations performed using the isocon method [75,76] revealed some depletion in major
and trace elements, compared with fresh shoshonitic basalt. By contrast, in some
hydrothermally‐altered basaltic scoria and lava ejecta, the original porphyritic texture is
almost completely obliterated, pseudomorphic phenocrysts can be barely recognized, and
glass is almost entirely replaced by secondary phases, mainly Mg, Al and Na hydrous
sulphate or hydroxysulphate minerals, precipitated during hydrothermal leaching of the
extrusive or subvolcanic rocks. The whole‐rock chemistry of these strongly
hydrothermally‐altered volcanics [21] is in agreement with the recognized mineral phases,
showing a general depletion in major oxides with the exception of those that are major
constituents of the secondary mineral phases (Mg, Al, Na, S, Cl, F). Veins and zones of
cristobalite and amorphous silica can also be observed at the micro‐mesoscale.
Some of these ejecta can be considered true fumarolic incrustations and sublimates
(similar to those investigated by Coradossi and Corsini [73]) due to exposure to oxidized
volcanic gas in solfatara, while others are hydrothermally‐altered volcanic and
subvolcanic rocks of the Stromboli edifice belonging to the intermediate argillic, advanced
argillic or silicic alteration [77,78], likely representing the rocks of the shallow
hydrothermal zone of the volcano which could interact subsurface with the rising basaltic
magmas of the volcano. These kinds of hydrothermal ejecta are considered the aluminum‐
enriched early protoliths of some igneous pyrometamorphic ejecta of Stromboli [21,22].

3. Materials and Methods

The unique sulphide‐rich composite porcellanite–buchite B1 xenolith (Figure 2)
erupted as a fragment during the 5 April 2003 paroxysm of Stromboli [79] and was
sampled as a loose block on the surface by Antonella Bertagnini (INGV—Istituto
Nazionale di Geofisica e Vulcanologia, Italy) at ca. 400 m of altitude in the western part of
the island, NE of Ginostra village (Figure 3a). In this paroxysm, several lithic blocks
erupted, mainly lavas and subvolcanic dolerites [53], these latter often coated with the LP
pumices, the main juvenile component, and the HP scoria.
Although already investigated by Del Moro et al. [21], the B1 sample—mainly termed
as a cordierite–plagioclase facies by these authors—deserved to be further studied
because of the distinctive occurrence of sulphide globules. White porcellanite and dark
buchite that intimately mingled each other suggested a working hypothesis of complex
multistage igneous pyrometamorphic events coupled with high temperature mineral–gas
reactions. The tridymite–clinopyroxene facies in the B1 composite xenolith, mentioned by
Del Moro et al. [21], corresponds to negligible parts of the sample and is therefore beyond
the scope of the present paper. In this work, quantitative spot analyses of discrete minerals
and glasses were carried out by a Hitachi 4300 FESEM (Hitachi, Schaumburg, IL, USA)
equipped with an Oxford Instruments INCA EDS analyser with a spatial resolution of
about 3 to 5 μm. The relative analytical error for major elements in Table 1 is 1–2%. The
system was calibrated against well characterised reference minerals (Astimex).
QEMSCANTM (Quantitative Evaluation of Minerals by Scanning Electron Microscopy)
mineral and element mapping were undertaken at the Centre for Advanced Microscopy
at the Australian National University using a FEI QEMSCANTM automated SEM–EDS
Minerals 2021, 11, 639 8 of 21

system on polished samples (for analytical methods, see Sieber et al. [80]). Some bulk rock
and mineral analyses of B1 xenolith are taken from Del Moro et al. [21], where analytical
methods and standards can also be found.

Table 1. FESEM EDS analyses of porcellanite glass (PG) and buchite glass (BG) of B1 xenolith. The three last columns
represent the reference composition of the three glasses’ population (mean) of the glass (using 2 μm spots) for the
QEMSCANTM map of Figure 4: PG*: porcellanite glass mean population; HSG1*: High silica glass, mean population 1 in
the buchite; HSG2*: High silica glass, mean population 2 in the buchite.
Oxide PG PG PG PG PG PG PG BG BG BG BG BG BG BG BG PG* HSG1* HSG2*
SiO2 55.1 54.5 54.4 53.3 52.9 50.7 50.5 79.7 77.5 74.7 69.6 67.5 66.0 63.0 61.0 53.4 77.7 65.9
TiO2 0.28 0.57 0.42 0.32 0.46 0.33 0.33 0.55 0.51 0.96 0.32 0.49 0.40 0.55 1.26 0.32 0.52 0.68
Al2O3 37.3 37.3 38.0 39.0 39.3 42.2 42.3 11.1 13.0 14.2 17.0 17.3 20.8 19.0 20.1 39.0 13.0 18.7
FeOtot 0.92 1.02 0.85 0.88 1.03 0.85 0.94 0.64 1.04 0.97 1.75 1.46 2.20 2.78 2.07 0.87 1.04 1.26
MgO 0.23 0.34 0.56 0.33 0.49 0.27 0.32 0.20 0.24 0.33 0.41 0.64 3.27 1.78 1.22 0.33 0.23 0.70
CaO 0.49 0.49 0.43 0.59 0.52 0.53 0.57 0.37 0.60 0.74 0.92 0.69 0.69 1.46 1.42 0.59 0.60 0.91
Na2O 1.56 1.51 1.46 1.48 1.50 1.42 1.41 1.91 1.42 1.81 2.39 3.63 1.68 4.03 4.29 1.48 1.42 3.94
K2 O 3.70 3.76 3.53 3.65 3.45 3.17 3.21 5.54 5.30 5.94 5.99 7.60 4.40 7.16 7.23 3.65 5.30 7.70
P2O5 0.41 0.48 0.30 0.46 0.30 0.50 0.48 ‐ 0.35 0.37 0.80 0.55 0.57 0.23 1.41 ‐ ‐ ‐
SO3 ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ 0.84 0.18 ‐ ‐ ‐ ‐ ‐ ‐
Total 99.99 99.97 99.95 100.01 99.95 99.97 100.06 100.01 99.96 100.02 100.02 100.04 100.01 99.99 100 99.64 99.81 99.79

The distribution of sulphide globules in a 5 mm diameter core of B1 was also mapped

by high resolution (2.3 μm voxel) X‐ray μCT using custom facilities in the Department of
Applied Mathematics at the Research School of Physics and Engineering at the Australian
National University. Results are provided in the supplementary material (Video S1: 3D
data visualization of the X‐ray μCT investigation on a 5 mm diameter core of the
porcellanite–buchite sample; Table S1: sulphide globules size and abundance
distribution).

4. Results
4.1. Mineral Phases and Glass Compositions
The composite porcellanite–buchite sample B1 is a cryptocrystalline to glassy
pyrometamorphic rock where cordierite, mullite/sillimanite, aluminous spinel and
corundum represent the main recognized silicate and oxide minerals [21], together with
abundant sulphide globules. With respect to analysis of the context of the evolution of the
composite xenolith, it is important to note that the basalt coating the xenolith is
represented by the two juvenile magmas commonly erupted during paroxystic eruptions
of Stromboli, namely LP and HP basalts (Figure 2). In the high resolution QEMSCANTM
map of Figure 4 (ca 1.25 cm × 1.75 cm) that shows the distribution of mineral phases (as
colour variations) across the B1 sample, the main silicates, oxides and sulphides are em‐
phasized, and it is evident that most of the xenolith consists of silicate glass.
Minerals 2021, 11, 639 9 of 21

Figure 4. A large (1.25 cm × 1.75 cm) QEMSCANTM area (step from one pixel to the next is 4.8 μm) of the composite
porcellanite–buchite xenolith (B1). The inset highlights the acicular needles that change from corundum to mullite, Al–
spinel and high An% plagioclase + glass marking the contact between the xenolith (left) and the LP–HP basaltic magma
(to the right, not present in this figure). The anorthite–labradorite colour indices provide the plagioclase composition
between these end‐members for both phenocrysts and glass.

Based on quantitative EDS analyses using spots selected in order to minimise the
inclusion of nano scale mullite crystals, the glass compositions were roughly subdivided
(Table 1; Figure 4), on average, into: (i) lower silica porcellanite glass (PG*) also crowded
by micro‐nano mullite and sillimanite and consisting of 53.4 wt.% SiO2 and 39.0 wt.%
Al2O3, (ii) higher silica glass 1 (HSG1*) in the buchite portions and characterized by 77.7
wt% SiO2 and 13.0 wt.% Al2O3 and (iii) higher silica glass 2 (HSG2*) always characterizing
the buchite, showing 65.9 wt.% SiO2 and 18.7 wt.% Al2O3. Necessarily, the overall
composition of the evolved melts would have been higher in Al2O3 given the
crystallization of abundant mullite within the evolved glass. It is worth noting that the
total oxide concentration near 100% in Table 1 could be explained by water driven off at
the very high temperature (≥1000 °C) and therefore almost entirely lost. The efficiency of
such loss could be due to the open‐system process (see next Chapters). Moreover, the
abundance of micro–crypto crystalline mullite precluded satisfactory ICP–MS spot
analyses of glass.
Minerals 2021, 11, 639 10 of 21

As commonly found in high‐T low‐P pyrometamorphic rocks [81,82], cordierite is

characterized by a peculiar high K2O content (0.2–1.2 wt.%; [21]) and is mostly concen‐
trated in the higher silica glass of the buchite. As investigated by Del Moro et al. [21], all
the crystals of cordierites studied show orthorhombic symmetry, although a transfor‐
mation from precursor hexagonal indialite is considered likely.
The white porcellanite and dark buchite should be considered as distinct rock do‐
mains of the sample. A very thin crystalline to glassy selvage (previously defined as mul‐
lite–plagioclase palisade by Del Moro et al. [21]) made of acicular mullite–corundum, alu‐
minous spinel and plagioclase + glass, marks, to a depth of maximum 4 mm (Figure 4),
the contact with the juvenile basalt mantling the ejecta. Spinels in the selvage have lower
Al2O3 (43.7–63.9 wt.%) and higher FeOtot (18.8–38.8 wt.%) with respect to those in the por‐
cellanite–buchite main xenolith (Al2O3 59.9–64.0 wt.%; FeOtot 12.3–12.4 wt.%) [21]. This can
be the result of Fe‐enrichment by diffusion processes from the basaltic magma at the con‐
tact with the xenolith. As shown in Figure 4, plagioclase in the selvage, forming tabular
and prismatic crystals up to 500 μm in length, is characterized by a relatively high content
of anorthite (from An82 to An92; [21], mostly emphasized as labradorite or anorthite in Fig‐
ure 4) and FeOtot 0.5–2.3 wt.%. The relatively high to very high Al‐content throughout the
composite xenolith is highlighted in Figure 5a, whereas the crystalline to glassy selvage
at the contact with the main porcellanite–buchite is characterized by a strong Ca enrich‐
ment and a relatively high content of Fe with respect to Mg (Figure 5b–d).

Figure 5. QEMSCANTM element maps showing relative element concentrations (a) Al, (b) Ca, (c) Fe,
and (d) Mg colour variations across the mapped region of B1 shown in Figure 5.

Intergrown low‐ and high‐Cu pyrrhotite and chalcopyrite were detected and
mapped within sulphide globules in Figures 4, 6 and 7. These sulphide globules only
crowd the buchite portion of the composite ejecta, and this is very well shown in Figures
6a,b and 7a where the bright sulphide globules in the FESEM backscatter images are ab‐
sent in the porcellanite portions. This distribution clearly links the sulphide formation to
a distinct petrogenetic stage of the evolution of the composite xenolith during the for‐
mation of the higher‐silica glass. FESEM images of the sulphide globules on the surface of
shards of B1 sample in the buchite portion are shown in Figure 6c–d. According to high
resolution X‐ray μCT imaging (Figure 8a and Video S1) performed on a 5 mm diameter
core of the porcellanite–buchite xenolith, about 1.1 million of sulphide globules (>99.5%)
range from <2.5 to 1600 μm in diameter although more than 50% have diameters <34.5μm
(Table S1). The two porcellanite and buchite glasses are immiscible as evidenced by the
slightly angular, cuspate–convolute margins between them, suggesting a liquid–liquid in‐
teraction (Figures 2, 4, 6, and 7).
Minerals 2021, 11, 639 11 of 21

Figure 6. FESEM backscattered image of the composite B1 xenolith at lower (a) and higher (b) mag‐
nification, showing intimately mingled porcellanite and buchite. The two portions of the pyromet‐
amorphic xenolith are also distinguished by the presence of sulphide globules only in the buchite
portions as further emphasized in the X‐ray μCT imaging provided in Figure 8a and Video S1.
Sharpened FESEM images of sulphide globules exposed on the surface of a buchite glass shard from
sample B1, having a size of about 2 μm and 8 μm are shown in (c) and (d), respectively.

Mineral phases, different glass compositions and the sulphide globules distribution
in the B1 sample are also shown by the QEMSCANTM mineral maps of Figure 7b–d, where
the increasing silica content in the glass is shown by different grey scale values as verified
by EDS spot analysis for sites as free as possible from mullite microcrystals that developed
during glass quenching. The porcellanite has much lower SiO2 and higher Al2O3 much
denser mullite distribution with respect to the buchite and contains no sulphide globules.
Strong depletion of divalent ions (FeO, MgO, CaO) from the glass occurs with increasing
silica (Table 1). In the buchite part of the xenolith, Na2O concentration ratios relative to
Al2O3 have a wide range exceeding those of the porcellanite, while K2O in the higher silica
glass is strongly enriched (Table 1). The higher‐silica glass also contains dispersed micro‐
crystals of mullite but at much lower abundance than in the porcellanite. A pseudomor‐
phic clinopyroxene phenocryst of the early protolith of the xenolith is emphasized in Fig‐
ure 7d, almost completely replaced by cordierite and mullite.
Minerals 2021, 11, 639 12 of 21

Figure 7. Backscatter FESEM image with the bright sulphide globules in the buchite portion (a); QEMSCANTM map (step
size of one pixel to the other is 1.3 μm) of the B1 porcellanite–buchite composite xenolith (b); close–up of the QEMSCANTM
map (buchite portions): sulphide globules (pyrrhotite, Low‐Cu pyrrhotite and High‐Cu pyrrhotite) (c); pseudomorphic
clinopyroxene of the early protolith of the xenoliths mainly replaced by cordierite and mullite (d). For abundance and size
distribution of the sulphide globules, see also X‐ray μCT scan data in Figure 8a and presented in the Supplementary
Material (Video S1, Table S1).

Pyrrhotite, low‐Cu pyrrhotite and high‐Cu pyrrhotite occur together within the sul‐
phide globules (close‐up of Figure 7c). In detail, they consist of a three‐composite phase
of cupriferous Fe–S containing, respectively, 1–4, 8–9 and 21–30 mole% Cu. Element map‐
ping data integrated over the two‐dimensional cross section of the larger globules gives
10.5 mole% Cu and 39.5 mole% Fe that may be taken as a first estimate of the unmixed
original globule composition. Zinc is the only other significant element up to 1 mole%.
Some globules are embayed with irregular coatings containing Pb and As sulphide. Un‐
mixing of the sulphide phases to grain sizes less than laser–ablation spot size (20 μm)
precluded use of this method to quantify the partitioning of metals between the globules
and the surrounding glass. The abundance of sulphide globules is not fully expressed in
a 2D polished section due to steric effects (Figure 8a) but becomes very clear in a video of
the X‐ray μCT scan of 3D data (Video S1).
The ternary sulphide phase diagram (Figure 8b) suggests that, for an initial sulphide
molar composition of Cu:Fe:S = 10.5:39.6:49.9 mole% such as that found for some of the
Cu–pyrrhotite, the globule temperature was close to 1000 °C. Following the experimental
data of Vaughan and Craig [83] for the Cu–Fe–S system (Figure 8b) at 700 °C, melts are
entirely quenched to an exsolution assemblage comprising an intermediate solid solution
phase (ISS) and chalcopyrite (ccp) and other phases close to CuFeS2 and a solid solution
Minerals 2021, 11, 639 13 of 21

around bornite (bnSS). By contrast, at 1000 °C, the Cu–Fe–S system is dominated by the
presence of an extensive field of a single sulphide liquid crossing the central part of the
ternary diagram (Figure 8b). The inferred sulphide molar composition of the globules
found in the pyrometamorphic ejecta B1 is close to the limit of the Cu–poor end member
liquid at 1000 °C. In this way, the spherical form of the globules and phase unmixing in‐
dicate that the sulphides were originally molten in the silicate melt.

Figure 8. (a) Slices of the composite porcellanite–buchite xenolith of Stromboli through the 3D X‐ray μCT data for a 5 mm
diameter core (high resolution 2.3 μm voxel size). They show the sulphide globules (as bright spots) in xz planes as we see
flying through the 3D data in the video (see Video S1) where their abundance is far larger than how it appears on a 2D
polished section surface due to steric effects (polished sections only expose minerals at a single surface so that fine particles
beneath the immediate surface are not visible); (b) phase relations in the Cu–Fe–S system at 700 °C and 1000 °C from
Vaughan and Craig [83] adapted from Barton and Skinner [84]. L = liquid; SS = solid solution; bn = bornite; ISS = interme‐
diate solid solution; py = pyrite; po = pyrrhotite; ccp = chalcopyrite. The yellow star is the approximate bulk composition
of the sulphide globules quenched as immiscible liquid in the buchite portion of the B1 xenolith. The composition of the
sulphide globules corresponds to a theoretical pyrrhotite—chalcopyrite tie line.

4.2. Major and Trace Elements Bulk Rock Composition

Bulk–rock compositions reported by Del Moro et al. [21] for the B1 xenolith show an
increase of SiO2 (56 to 68 wt.%), Na2O (1.5 to 1.9 wt.%), K2O (3.6 to 4.7 wt%) and sulphur
(0.1 to 0.3%), and a decrease of Al2O3 (34 to 19 wt.%) from the white porcellanite to the
dark buchite. This is also demonstrated by a bulk rock analysis [21] performed from a
mixture of the composite white porcellanite and dark buchite (M–PB) showing an inter‐
mediate major element composition. Thus, a relatively high‐Al low‐Si white porcellanite
(HALS–WP) and low‐Al high‐Si (LAHS–DB) dark buchite can be clearly defined. This
agrees with the glass compositions recognized here (Table 1; Figures 4 and 7). Low CaO
(0.7–1.0 wt.%) characterize both HALS–WP and LAHS–DB. As reported by Del Moro et
al. [21], REE and incompatible trace element patterns (respectively normalized to chon‐
drites and primordial mantle) of the B1 xenolith mostly match the composition of the
trachytes of the Upper Vancori that may have undergone hydrothermal leaching prior to
burial Neostomboli and Recent Stromboli volcanics.
In the ternary diagram of Figure 9, the buchite suite from Del Moro et al. [21] is en‐
tirely distributed within a wide spectrum of hydrothermal alteration, namely intermedi‐
ate‐advanced argillic, phyllic‐propylitic and silicic, taken as reference from Vulcano Is‐
land, in the same Aeolian Archipelago (and same subduction‐related volcanism) to which
Stromboli Island belongs [77]. Bulk rock and glass compositions of the B1 porcellanite–
buchite xenolith follow a linear trend between the SiO2 and (Al, Fe)2O3 + (Na, K)2O
Minerals 2021, 11, 639 14 of 21

components and show the same values of (Fe + Mg + Mn + Ca)O + TiO2 + P2O5. The chem‐
ical trends of the B1 xenoliths in Figure 9 could therefore be the result of the protolith
signature (lavas or pyroclastics of Stromboli which suffered hydrothermal leaching) and
the magmatic processes of the open system igneous pyrometamorphism leading to pro‐
tolith transformation. By contrast, bulk–rock and glass compositions of the Stromboli
buchites interpreted as deriving from deeper continental crust [17] show an increasing
trend of (Fe + Mg + Mn + Ca)O + TiO2 + P2O5, decreasing SiO2 and relatively uniform (Al,
Fe)2O3 + (Na, K)2O.

Figure 9. Ternary diagram (from Grapes [1]) of the major element oxides in mol.% for bulk rock compositions and glass
of the investigated porcellanite–buchite xenolith (B1) and the buchite suites from Del Moro et al. [21] and Salvioli–Mariani
et al. [17]. The B1 porcellanite–buchite composite sample is highlighted with its three analyses (end members HALS–WP,
LAHS–DB and the intermediate composition M–PB). Data from Stromboli HP basalt whole rocks [37] and glass [85] are
also reported for comparison.

5. Discussion
A unique mineralogical feature of the investigated composite porcellanite–buchite
xenolith, B1, from Stromboli is the presence of abundant sulphide globules (pyrrhotite–
chalcopyrite). Their occurrence is incompatible with the estimated oxygen fugacity of the
LP basalts (between NNO + 0.5 and NNO + 1 [28–31]) and with the oxidizing condition of
the shallow acid–sulphate hydrothermal system of the volcano. Sulphide globules were
previously recognized in other buchite ejecta of Stromboli [17] but never detected in the
HP basalts or their shallow subvolcanic counterparts, i.e., the dolerites. In these latter,
however, both Ti‐magnetite and ilmenite are present [53], and therefore an oxygen fugac‐
ity slightly lower than that of the LP basalt can be inferred.
Sulphate minerals (nor elemental sulphur) are not present in the B1 xenolith so that
sulphide formation is not a consequence of a disproportionation reaction. Development
of immiscible sulphide melt from a precursor assemblage relatively poor in sulphur
Minerals 2021, 11, 639 15 of 21

requires addition of sulphur from volcanic gas to maintain a gas‐saturated melt and re‐
duction of the dissolved SO2 to S−2. We thus suggest that the sulphide globules are the
product of open‐system reaction between the evolving xenolith melt and the high flux of
magmatic gas interacting with exposed altered Vancori volcanics. Magmatic gas at Strom‐
boli, as for other basaltic volcanoes, is a mixture dominated by H2O and high in CO2, SO2,
H2 and HCl, with H2S as a minor component of the total sulphur [27,64]. These gases are
soluble in basaltic melts [86] so that, in an open vent system, the xenolith–basalt melt
phase may be considered to have been maintained at gas saturation within the chemically
and thermally open‐system defined by the xenolith and its external basalt–gas flux to‐
gether with the diffusion of components including calcium and sulphur into and out of
the partially melted white porcellanite (possibly through observed cracks), thus forming
the dark buchite portions. Cuspate–convolute margins between white porcellanite and
dark buchite implies a liquid–liquid interaction, along permeable areas (cracks) of the
early porcellanite induced by the flowing HP basaltic magma–gas eruptive mixture.
Above 1000 °C, the favourability of a reaction between a flux of high temperature SO2 and
basaltic melt has been demonstrated experimentally (Henley R.W. unpublished data) and
similarly for basaltic glasses [87]. Dissolution of plagioclase into the evolving buchite melt
releases Ca as a CaClmelt species from plagioclase due to incongruent reaction with HCl
from the magmatic gas. There is a consequent release of H2 into the melt with net localized
lowering of fO2 coupled with the reduction of dissolved SO2 that, with the simultaneous Fe
release during cordierite formation, drives sulphide formation. The source of Cu for the
sulphide melt is paradoxical, given its presence in only trace quantities in the primary
xenolith material and the basaltic melt. As discussed elsewhere (e.g., [27]), the common
occurrence of copper in immiscible sulphide melts in volcanic systems suggests that it is
scavenged along with SO2, HCl, etc. from the gas phase as a dissolved component into the
xenolith melt. This is supported by the data of Allard et al. [88] for the emission rates of
copper and other metals from Stromboli.
We suggest that open‐system igneous pyrometamorphism (i.e., transformation
driven by both basaltic magma and high‐T gas flux) led to the formation of the immiscible
sulphide globules. The formation of these latter is spatially and temporally associated
with the buchite parts of the composite xenolith: (i) calcium loss from plagioclase pheno‐
crysts and conversion of ferromagnesian minerals to cordierite, (ii) partial melting of the
early porcellanite and exposure of the composite xenolith to high‐T gas flux in the active
basaltic vent system. This final process was however preceded by a complex petrogenetic
history including: a) hydrothermal leaching of fresh volcanics at relatively low‐T (ad‐
vanced argillic alteration facies) and b) high‐T igneous pyrometamorphism of a hydro‐
thermally‐altered protolith, leading to an early porcellanite.
B1 composite xenolith formation may have occurred at typical pyrometamorphic
temperatures >1000 °C which were kept high by the constant flux of volcanic gas in con‐
junction with basalt melt through the vent system [89].
On Stromboli volcano, the volume of the pyrometamorphic ejecta is quite small rela‐
tive to the volume of erupted basaltic magma and all other types of lithics [22,53]. The
presence of pyrometamorphic xenoliths is linked to major explosions or paroxysms of the
volcano and is dependent on the fact that one or more events of igneous pyrometamor‐
phism occurred on vent walls before those eruptions that carried the xenoliths up to the
surface. Thus, porcellanite or buchite ejecta can be found more frequently in persistently
active basaltic volcanoes such as Stromboli (rather than other active volcanos with long or
short periods of rest) because the open vent system and the persistent activity creates more
chances of (i) high‐T magma–wall rock interaction, (ii) spalling of subvolcanic vent system
wall rocks and (iii) high‐T gas–solid interactions allowing pyrometamorphic xenoliths to
be formed and continuously transformed during vent system processes shortly (we infer
months) before being erupted.
Minerals 2021, 11, 639 16 of 21

Space‐Time Inferences on the Formation of the Porcellanite‐Buchite Xenolith

As the investigated porcellanite–buchite B1 composite xenolith was erupted during
the paroxysm of 5 April 2003, the petrogenetic processes leading to its formation are pro‐
posed to be spatially and temporally associated with the shallow subvolcanic system of
Stromboli, before and during the Stromboli 2002–2003 eruptive crisis, an effusive eruption
which lasted six months, from 28 December 2002 to July 2003 [90–92]. The paroxysm [79]
occurred while the lava effusion was still in progress in the lower flanks of the Sciara del
Fuoco.
With respect to the general two‐stage model (initial hydrothermal leaching and sub‐
sequent igneous pyrometamorphism) of the pyrometamorphic process proposed by Del
Moro et al. [21], the petrogenetic history of the B1 porcellanite–buchite sample is more
complex and requires a multistage process (Figure 10).

Figure 10. Simplified sketch (in four stages, a–d) explaining the petrogenetic history of the B1 porcellanite–buchite xenolith
(erupted during the 5 April 2003 paroxysm, stage d) in the subvolcanic environment of Stromboli volcano. The sketch is
envisaged for processes that occurred before (stage a) and during the 2002–2003 eruptive crisis of Stromboli (from January
to late March 2003, stages b–c). The 2002–2003 eruptive crisis included an effusive eruption lasting six months (from 28
December 2002 to July 2003; [90,91]) and the violent explosion (paroxysm) that occurred on 5 April 2003 [79] while the
lava effusion was still in progress. During this eruptive crisis, the normally persistent summit activity ceased from January
to late March 2003, whereas the HP basaltic magmas continued to be outpoured as lavas from vents in the lower flanks of
the volcano, along the Sciara del Fuoco [90].

The first stage is the formation of the early porcellanite by igneous pyrometamor‐
phism of magma conduit wall rocks and their spalling off due to the turbulence of the
rising HP basaltic magma (Figure 10a), which likely occurred before the 2002–2003 erup‐
tive crisis. The early porcellanite protolith, having high‐Al content, could have been por‐
phyritic lavas or pyroclastics of Stromboli affected by an advanced argillic alteration. Af‐
ter the onset of the flank effusive activity on 28 December 2002, the mild strombolian erup‐
tions at the summit crater area ceased until late March 2003 [90,92], although the typical
Very Long Period seismicity linked to the gas slugs (generally driving the mild explosions
of the persistent activity) continued to be present [91]. As a matter of fact, continuous gas
percolation and basaltic dolerite formation were more frequent in the uppermost conduit
Minerals 2021, 11, 639 17 of 21

system during January–late March 2003 [53]. The presence of (i) abundant miarolitic cav‐
ities and (ii) some anomalous metal trace elements in the dolerite ejecta deriving from the
shallow crystallization of the HP basalts [53] emphasize the role played by high tempera‐
ture gas fluxes even during the absence of mild Strombolian eruptions at the crater sum‐
mit area. In addition, abundant rocks of the vent system engulfed the shallow subvolcanic
system at the beginning of the eruptive crisis on 28 December 2002 [92], possibly including
porcellanite blocks as well (Figure 10b).
The HP basaltic magma started to intrude again in the uppermost vent system only
in late March 2003 (Figure 10c), resuming the persistent crater area activity [91]. During
the stages envisaged in Figure 10b,c the early porcellanite may have transformed into a
composite xenolith with the developing of the buchite portions enriched in the sulphide
globules. The B1 sample was finally ejected together with HP and LP magma, abundant
loose basaltic dolerite clasts, doleritic breccias and other type of lithics [53] during the 5
April 2003 paroxystic eruption (Figure 10d).
The thin crystalline to glassy selvage characterized by corundum–mullite needles,
Al‐spinel and high An% plagioclase between the xenolith and the LP–HP basalt coatings
may only represent the very last syneruptive thermometamorphic reaction, just before the
xenolith was ejected in the 5 April 2003 paroxysm. Similar selvages are common at the
rims of Al‐rich xenoliths or pyrometamorphic rocks formed at the contact with basaltic
magmas (e.g., [1,93,94]). Bowen [95] was the first to argue that the reaction of an alumi‐
nous xenolith with a basic magma would cause excess precipitation of high An% plagio‐
clase from the magma and Preston et al. [94] suggest the reaction:
CaMgSi2O6 + 2Al2O3 → CaAl2Si2O8 + MgAl2O4 (1)
with clinopyroxene considered the saturated component of the basaltic magma and the
Al2O3 deriving from the aluminous xenolith.

6. Conclusions
The occurrence of cupriferous immiscible sulphide globules in the investigated py‐
rometamorphic buchite–porcellanite xenolith from Stromboli is paradoxical, given the
general absence of sulphides in the Stromboli erupted basalts. In this paper, we have
shown that sulphide globules’ formation in the buchite portions of the composite xenolith
was coupled with a loss of calcium from plagioclase, pyrometamorphism of ferromagne‐
sian minerals to cordierite–mullite, and melt formation through melting of an early por‐
cellanite deriving from the shallow vents/conduit wall rocks (hydrothermally altered vol‐
canic products). This occurred in the presence of contemporary basalt melt and high‐T
volcanic gas flux. The loss of Ca emphasizes the open‐system context for exchange of re‐
active gas species between the external volcanic gas flux and the evolving buchite melt. It
is suggested that sulphide formation is a consequence of the reaction of HCl dissolved
into the melt from the gas phase, Cl stabilization as Ca chloride gas species releasing H2
into the melt and consequent reduction of dissolved SO2. The speciation of sulphur in
silicate melts is controversial, but recent advances using X‐ray Absorption Near–Edge
Spectroscopy (XANES) [96] suggest that increasing FeO content of a melt favours an in‐
crease in the S2− concentration. Dissolution of ferromagnesian phenocrysts into the evolv‐
ing buchite melt coupled with the exchange of SO2 into the melt from the gas phase then
drives the formation of sulphide melts to be quenched as immiscible sulphide globules.
Buchite portions of the B1 sample melts are relatively Cu‐rich (and often have CuFeS glob‐
ules), and this suggests that the CuS component of the sulphide globules in the buchite
glass may also be due to partitioning of Cu from the gas flux into the melt.
Phase relations and bulk–rock compositions suggest that the evolutionary stages of
the porcellanite–buchite assemblages occurred at relatively low pressures (a few tens to
hundred bars at most) above 1000 °C and perhaps as high as 1150 °C [1,17,21], commen‐
surate with observed vent temperatures [97] and in agreement with the highest tempera‐
ture of the igneous pyrometamorphism (Figure 1). This process includes an initial igneous
Minerals 2021, 11, 639 18 of 21

pyrometamorphism stricto sensu (porcellanite) and subsequent open‐system exchange of

reactant SO2–HCl–H2 gas and CaCl species between the evolving xenolith melt and the
general flux of volcanic gas and basaltic melt (buchite) in the shallow Stromboli vent sys‐
tem. In this way, both a basaltic magma and a gas–flux reaction near magmatic tempera‐
ture can induce igneous pyrometamorphism (and metasomatism) in a subvolcanic envi‐
ronment through magmatic processes. The B1 composite xenolith has a very complex
petrogenesis so that clearer resolution of its components and element zonation patterns
(also of additional ejecta of Stromboli derived from open‐system igneous pyrometamor‐
phism) awaits further work including experimental determination of relative element dif‐
fusivities during reactive mass transfer processes between high temperature gas mixtures
and silicate glasses and basaltic magma–xenolith interaction.

Supplementary Materials: The following are available online at www.mdpi.com/arti‐

cle/10.3390/min11060639/s1, Video S1: 3D data visualization of the X‐ray μCT investigation on a 5
mm diameter core of the porcellanite–buchite sample; Table S1: datable Sta on sulphide globules
abundance and size distribution.
Author Contributions: Conceptualization, A.R. and R.W.H.; methodology, A.R., M.T., F.J.B., S.D.M.
and R.W.H.; materials, S.D.M.; validation, A.R., M.T., F.J.B., S.D.M. and R.W.H.; formal analysis, (X‐
ray μCT, FESEM and QEMSCANTM mineral mapping) R.W.H. and F.J.B.; investigation, A.R., M.T.,
F.J.B., S.D.M. and R.W.H.; data curation, A.R., M.T. and R.W.H.; writing—original draft preparation,
A.R., M.T. and R.W.H.; writing—review and editing, A.R., M.T., F.J.B., S.D.M. and R.W.H.; visuali‐
zation, A.R. and M.T.; supervision, A.R. and R.W.H.; project administration, A.R. and R.W.H. All
authors have read and agreed to the published version of the manuscript.
Funding: R.W.H. and F.J.B. note initial funding from the Australian Research Council (Penelope L.
King). Department of Pure and Applied Sciences (DISPEA, University of Urbino) financially sup‐
ported M.T. with a postdoc grant.
Data Availability Statement: All data used in this work are reported in the main text or in the
Supplementary Material.
Acknowledgments: Michael Turner and Hoger Averdunk are thanked for X‐ray CT scanning and
data processing of the investigated B1 sample. R.W.H. acknowledges the pleasure of being intro‐
duced to Stromboli by Volcano Discovery (https://www.volcanodiscovery.com/) and thanks Justin
Whyte for logistic support. Two anonymous reviewers and Guest Editor of the special issue (Monica
Piochi) are thanked for comments and suggestions that really helped to improve an early version of
the manuscript.
Conflicts of Interest: The authors declare no conflict of interest.

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